[go: up one dir, main page]

WO2018009591A1 - Radiation curable primer adhesive - Google Patents

Radiation curable primer adhesive Download PDF

Info

Publication number
WO2018009591A1
WO2018009591A1 PCT/US2017/040793 US2017040793W WO2018009591A1 WO 2018009591 A1 WO2018009591 A1 WO 2018009591A1 US 2017040793 W US2017040793 W US 2017040793W WO 2018009591 A1 WO2018009591 A1 WO 2018009591A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
chlorinated
monomer
diacrylate
meth
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2017/040793
Other languages
French (fr)
Inventor
Bob Chang
Vincent CHEVALIER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Worthen Industries Inc
Original Assignee
Worthen Industries Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Worthen Industries Inc filed Critical Worthen Industries Inc
Priority to EP17824844.9A priority Critical patent/EP3481902A4/en
Priority to CN201780041776.XA priority patent/CN109476929B/en
Publication of WO2018009591A1 publication Critical patent/WO2018009591A1/en
Priority to US16/238,829 priority patent/US11174414B2/en
Anticipated expiration legal-status Critical
Priority to US17/500,369 priority patent/US20220041892A1/en
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C08F255/023—On to modified polymers, e.g. chlorinated polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/002—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers modified by after-treatment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09J133/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2437/00—Clothing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00—Presence of polyolefin
    • C09J2423/04—Presence of homo or copolymers of ethene
    • C09J2423/046—Presence of homo or copolymers of ethene in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2427/00—Presence of halogenated polymer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2431/00—Presence of polyvinyl acetate
    • C09J2431/006—Presence of polyvinyl acetate in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2467/00—Presence of polyester
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2475/00—Presence of polyurethane

Definitions

  • the present invention relates generally to primers and adhesives for Ethylene-vinyl acetate (EVA) . More particularly the present invention relates to 100% solids compositions that function as one or both of an adhesive and primer on an EVA surface .
  • EVA Ethylene-vinyl acetate
  • a 100% solids composition operable at room temperature and capable of radiation curing is provided.
  • This composition, and the various embodiments of it disclosed herein, is particularly suited for use in bonding EVA to a substrate.
  • the composition has a monomer, a chlorinated compound, and a photo-initiator allowing radiation curing.
  • the monomer is selected to be at least one of a (meth) acrylate monomer and (meth) acrylate functional urethane oligomer.
  • the chlorinated compound is selected to be at least one of a chlorinated polyester, chlorinated rubber, and chlorinated polyolefin.
  • composition may have 10-50% hexanediol diacrylate as the monomer; 10-40% chlorinated polyester as the chlorinated compound; 10-30% cyclic aliphatic diacrylate; 1-5% acidic methacrylate ; and 1-5% photoinitiator .
  • the composition may have 10-50% hexanediol diacrylate as the monomer; 10-40% chlorinated polyester as the chlorinated compound; 10-30% 5-
  • the composition may have 60-99% methyl methacrylate as the monomer; 0-20% hexanediol diacrylate; 10-20% chlorinated polyolefin as the chlorinated compound; 1-20% acidic methacrylate; 1-5% NVC; and
  • composition may have 10-30% hexanediol diacrylate as the monomer; 10-70% acrylic polymer; 10-20% chlorinated polyester as the chlorinated compound; 1-5% acidic methacrylate ; and 1- 5% photoinitiator .
  • the composition may have 10-40% hexanediol diacrylate as the monomer; 10-40% chlorinated polyester as the chlorinated compound; 10-20% cyclic aliphatic diacrylate; 10-20% BCEA; 1-10% NVC; and 1-5% photoinitiator .
  • composition may have 10-40% hexanediol diacrylate as the monomer; 10-40% chlorinated polyester resin as the chlorinated compound; 1-5% acidic methacrylate; 10-20% BCEA; 1-10% NVC; and 1-5% photoinitiator .
  • the composition may comprise 10-50% of the monomer, the monomer being at least one of hexanediol diacrylate and methyl methacrylate.
  • the composition may have plurality of different (meth) acrylate functional urethane oligomers, the combination of the plurality of different
  • composition may comprise 10-30% cyclic
  • the composition may comprise the chlorinated compound in a composition of 10-40%.
  • This embodiment may also have a plurality of different (meth) acrylate functional urethane oligomers, which may comprise cyclic aliphatic diacrylate and acidic methacrylate.
  • This embodiment may also have a plurality of oligomers which comprises cyclic aliphatic diacrylate, acidic methacrylate, and modified epoxy
  • the composition may be used in a method of adhering EVA to a substrate.
  • This embodiment of use may have the steps of: obtaining the substrate; obtaining the ethylene- vinyl acetate; applying the composition of the present
  • composition-coated ethylene-vinyl acetate being bonded
  • composition used for this method of use embodiment may be any of the above noted embodiments, and/or any composition disclosed or described in the below detailed description, claims, abstract, and figures.
  • FIG . 1 provides a flow chart of an embodiment of use of the present inventive composition.
  • This invention includes an adhesive/primer composition for use with EVA having a 100% solids composition with 0% solvent added and may function as the adhesive itself so only the contact substrate requires an adhesive coat.
  • composition of the present invention removes unnecessary and potentially harmful VOC ' s from the worker and environment, eliminates the need for high temperatures that are required of hot-melt adhesives and their resulting difficulties, and also removes a step in the adhesion process of footwear
  • the present invention is usable at ambient room temperatures without any added temperature adjusting steps during use.
  • the present invention concerns a 100% solids, radiation curable adhesive formulation for adhesion to EVA. Further, in some embodiments, the present invention may be used as a primer as well as, or in alternative to adhesive. This formulation may have varying compositions, as discussed in detail below. However primarily the composition may
  • Photo initiators may be used to allow for low temperature UV or other radiation curing.
  • Other additives may be used to enhance functional features in various ways.
  • the formulations contemplated herein provide a number of advantages over the existing solutions.
  • the invention provides both an improved product and an improvement in manufacturing.
  • the 100% solids composition uses no volatile organic compounds
  • VOCs thereby making it a "greener” technology. Eliminating VOCs also creates a less hazardous and less expensive implementation. Further, the present invention eliminates steps from manufacturing by allowing room temperature, solvent free curing, and by eliminating the need for an adhesive directly applied to the cured adhesive/primer. Instead, an adhesive is only needed on the substrate to be applied to the EVA that is coated with the adhesive/primer of the present invention. This adhesive may be the composition of the present invention, or another adhesive. In many embodiments, a second adhesive is not needed, and the present inventive composition is sufficient to bond EVA to the substrate. These eliminated steps can result in cost savings and also energy savings (such as removal of an oven or less energy powering an incinerator), which in turn leads to a "greener" technology providing both a safer work environment and cost savings.
  • energy savings such as removal of an oven or less energy powering an incinerator
  • the composition may include either an acrylate or methacrylate, diluents, and a photo initiator.
  • a chlorinated compound may also be necessary, such as chlorinated polyester or chlorinated polyolefin .
  • the present invention composition requires a monomer, such as a (meth) acrylate monomer or (meth) acrylate functional urethane oligomer. Further, the composition
  • chlorinated compound such as a chlorinated
  • polyester chlorinated rubber, and/or chlorinated polyolefin. Additionally, the photo initiator allows for curing via, for example, UV radiation.
  • the primary features of the present inventive composition are the a monomer, selected to be at least one of a (meth) acrylate monomer and (meth) acrylate functional urethane oligomer; a chlorinated compound selected to be at least one of a chlorinated polyester, chlorinated rubber, and chlorinated polyolefin; and a photo initiator.
  • the specific compositions disclosed herein may, in many cases, have
  • chlorinated materials such as chlorinated polyester or chlorinated
  • polyolefins are designed to promote adhesion to specific substances. These substances include polyester, polypropylene, and other thermoplastic olefins (TPO) . EVA is different from and not related to these categories of materials. Therefore, the compositions of the present invention demonstrated the unexpected result of being highly effective with use on EVA as a primer and adhesive.
  • this invention is also thicker, because the solvent borne formulations tend to lay down only a monolayer as the solvent is driven off, leaving only solids. With 100% solid formulations, everything disposed on the EVA material remains. This allows better surface wet-out and penetration at the primed surface/adhesive interface. Overall, there is much more contact between layers compared to a thin monolayer with prior art solvent based compositions.
  • the composition may be applied to an EVA surface, such as a sole of a shoe.
  • This application may be by, for example, spraying, brushing, rolling, or the like.
  • the inventive composition may then be radiation cured- typically UV cured. Once cured the surface is ready to be bonded with an adhesive, for example a polyurethane adhesive-coated upper shoe portion.
  • This adhesive is then used to join the EVA with the mating surface.
  • an adhesive may be coated over the cured adhesive/primer of the present invention, but this additional adhesive is not required. Not including this second adhesive application cuts out a step when compared to the prior art process. It should be understood that this embodiment of use may use any variation of the inventive compositions disclosed herein without straying from the scope of this invention.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • General Chemical & Material Sciences (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The present invention involves a 100% solids, radiation curable adhesive formulation for adhesion to EVA. This formulation may have varying compositions, as discussed in detail herein. However primarily the composition may comprise at least a monomer, and a chlorinated additive. Photo initiators may be used to allow for low temperature UV or other radiation curing. Other additives may be used to enhance functional features in various ways. In use, the present invention may be coated on a surface of EVA and then cured, and may be adhered to a substrate using only a layer of adhesive on the substrate, in contrast to the structures of the prior art, which require at least two sided adhesive application, among other complexities.

Description

RADIATION CURABLE PRIMER ADHESIVE
BACKGROUND OF THE INVENTION
Field of the Invention
[0001]The present invention relates generally to primers and adhesives for Ethylene-vinyl acetate (EVA) . More particularly the present invention relates to 100% solids compositions that function as one or both of an adhesive and primer on an EVA surface .
Description of Related Art [0002]Working primers for EVA have traditionally been solvent borne. There are a few "waterborne" versions and also
radiation curable versions, but all actually contain some level of solvent. Additionally, traditional working primers require a direct coat of adhesive on top of the primer in order to function. Hot melt applications require high levels of heat, and lead to additional processing time when cooling.
[0003]Therefore, what is needed is a 100% solids formulation that may eliminate the need for solvent usage that may also function as an adhesive without the additional primer layer.
SUMMARY OF THE INVENTION
[0004]The subject matter of this application may involve, in some cases, interrelated products, alternative solutions to a particular problem, and/or a plurality of different uses of a single system or article. [0005] In one aspect of the present invention, a 100% solids composition operable at room temperature and capable of radiation curing is provided. This composition, and the various embodiments of it disclosed herein, is particularly suited for use in bonding EVA to a substrate. The composition has a monomer, a chlorinated compound, and a photo-initiator allowing radiation curing. In one embodiment of this aspect, the monomer is selected to be at least one of a (meth) acrylate monomer and (meth) acrylate functional urethane oligomer. In one embodiment of this aspect, the chlorinated compound is selected to be at least one of a chlorinated polyester, chlorinated rubber, and chlorinated polyolefin.
[0006] In a particular embodiment of this aspect, the
composition may have 10-50% hexanediol diacrylate as the monomer; 10-40% chlorinated polyester as the chlorinated compound; 10-30% cyclic aliphatic diacrylate; 1-5% acidic methacrylate ; and 1-5% photoinitiator .
[0007] In another embodiment of this aspect, the composition may have 10-50% hexanediol diacrylate as the monomer; 10-40% chlorinated polyester as the chlorinated compound; 10-30% 5-
35% cyclic aliphatic diacrylate; 1-5% acidic methacrylate; modified epoxy diacrylate; and 1-5% photoinitiator .
[0008] In yet another embodiment of this aspect, the composition may have 60-99% methyl methacrylate as the monomer; 0-20% hexanediol diacrylate; 10-20% chlorinated polyolefin as the chlorinated compound; 1-20% acidic methacrylate; 1-5% NVC; and
1-5% photoinitiator .
[0009] In a particular embodiment of this aspect, the
composition may have 10-30% hexanediol diacrylate as the monomer; 10-70% acrylic polymer; 10-20% chlorinated polyester as the chlorinated compound; 1-5% acidic methacrylate ; and 1- 5% photoinitiator .
[0010] In yet another embodiment of this aspect, the composition may have 10-40% hexanediol diacrylate as the monomer; 10-40% chlorinated polyester as the chlorinated compound; 10-20% cyclic aliphatic diacrylate; 10-20% BCEA; 1-10% NVC; and 1-5% photoinitiator .
[0011] In still another embodiment of this aspect, the
composition may have 10-40% hexanediol diacrylate as the monomer; 10-40% chlorinated polyester resin as the chlorinated compound; 1-5% acidic methacrylate; 10-20% BCEA; 1-10% NVC; and 1-5% photoinitiator .
[0012] In another embodiment of this aspect, the composition may comprise 10-50% of the monomer, the monomer being at least one of hexanediol diacrylate and methyl methacrylate. In a further particular example of this embodiment, the composition may have plurality of different (meth) acrylate functional urethane oligomers, the combination of the plurality of different
(meth) acrylate functional urethane oligomers making up 11-75% of the composition. In yet another particular example of this embodiment, the composition may comprise 10-30% cyclic
aliphatic diacrylate. In another particular example of this embodiment, the composition may comprise the chlorinated compound in a composition of 10-40%. This embodiment may also have a plurality of different (meth) acrylate functional urethane oligomers, which may comprise cyclic aliphatic diacrylate and acidic methacrylate. This embodiment may also have a plurality of oligomers which comprises cyclic aliphatic diacrylate, acidic methacrylate, and modified epoxy
diacrylate. [0013] In an embodiment of use this composition aspect, which includes, and is not limited to, use of any of the above noted composition embodiments of the aspect of the inventive
composition, the composition may be used in a method of adhering EVA to a substrate. This embodiment of use may have the steps of: obtaining the substrate; obtaining the ethylene- vinyl acetate; applying the composition of the present
invention at room temperature to the ethylene-vinyl acetate; curing the composition of claim 1 using a radiation;
contacting the ethylene-vinyl acetate having the composition of claim 1 applied to the substrate, the substrate and
composition-coated ethylene-vinyl acetate being bonded
together by an adhesive applied to the substrate. As noted, the composition used for this method of use embodiment may be any of the above noted embodiments, and/or any composition disclosed or described in the below detailed description, claims, abstract, and figures.
BRIEF DESCRIPTION OF THE DRAWINGS FIG . 1 provides a flow chart of an embodiment of use of the present inventive composition.
DETAILED DESCRIPTION
[0014] The detailed description set forth below in connection with the appended drawings is intended as a description of presently preferred embodiments of the invention and does not represent the only forms in which the present invention may be constructed and/or utilized. The description sets forth the functions and the sequence of steps for constructing and operating the invention in connection with the illustrated embodiments .
[0015] This invention includes an adhesive/primer composition for use with EVA having a 100% solids composition with 0% solvent added and may function as the adhesive itself so only the contact substrate requires an adhesive coat. The
composition of the present invention removes unnecessary and potentially harmful VOC ' s from the worker and environment, eliminates the need for high temperatures that are required of hot-melt adhesives and their resulting difficulties, and also removes a step in the adhesion process of footwear
manufacturing. The present invention is usable at ambient room temperatures without any added temperature adjusting steps during use.
[0016] Generally, the present invention concerns a 100% solids, radiation curable adhesive formulation for adhesion to EVA. Further, in some embodiments, the present invention may be used as a primer as well as, or in alternative to adhesive. This formulation may have varying compositions, as discussed in detail below. However primarily the composition may
comprise at least a monomer, and a chlorinated additive. Photo initiators may be used to allow for low temperature UV or other radiation curing. Other additives may be used to enhance functional features in various ways.
[0017]This 100% solids formulation does not require any
solvents, as is required of the prior art. The formulations contemplated herein provide a number of advantages over the existing solutions. For example, the invention provides both an improved product and an improvement in manufacturing. The 100% solids composition uses no volatile organic compounds
(VOCs) thereby making it a "greener" technology. Eliminating VOCs also creates a less hazardous and less expensive implementation. Further, the present invention eliminates steps from manufacturing by allowing room temperature, solvent free curing, and by eliminating the need for an adhesive directly applied to the cured adhesive/primer. Instead, an adhesive is only needed on the substrate to be applied to the EVA that is coated with the adhesive/primer of the present invention. This adhesive may be the composition of the present invention, or another adhesive. In many embodiments, a second adhesive is not needed, and the present inventive composition is sufficient to bond EVA to the substrate. These eliminated steps can result in cost savings and also energy savings (such as removal of an oven or less energy powering an incinerator), which in turn leads to a "greener" technology providing both a safer work environment and cost savings.
[0018] Speaking generally, in many, but not all embodiment of the present invention, the composition may include either an acrylate or methacrylate, diluents, and a photo initiator. For adhesion promotion to EVA, a chlorinated compound may also be necessary, such as chlorinated polyester or chlorinated polyolefin .
[0019] Typically, the present invention composition requires a monomer, such as a (meth) acrylate monomer or (meth) acrylate functional urethane oligomer. Further, the composition
requires a chlorinated compound such as a chlorinated
polyester, chlorinated rubber, and/or chlorinated polyolefin. Additionally, the photo initiator allows for curing via, for example, UV radiation.
[0020]As noted, the primary features of the present inventive composition are the a monomer, selected to be at least one of a (meth) acrylate monomer and (meth) acrylate functional urethane oligomer; a chlorinated compound selected to be at least one of a chlorinated polyester, chlorinated rubber, and chlorinated polyolefin; and a photo initiator. The specific compositions disclosed herein may, in many cases, have
different additives interchanged or used in other embodiments, without straying from the scope of the present invention. The following non-limiting examples provide approximate ranges of 100% solids compositions of the present invention that have been used to successfully bind EVA to a contact substrate:
[0021]Example 1
[0022]Example
[0023]Example
[0024]Example
[0025]Example
Figure imgf000009_0001
HDDA (hexanediol diacrylate)- monomer 10-40%
Ebecryl 438 - chlorinated polyester 10-40%
Ebecryl 130 - cyclic aliphatic diacrylate 10-20%
RCEA 10-20%
NVC 1-10%
Irgacure 500 1-5%
[0026] Example 66
HDDA (hexanediol diacrylate)- monomer 10-40%
Genomer 6050 - chlorinated polyester resin 10-40%
Ebecryl 168 - acidic methacrylate 1-5%
CEA 10-20%
NVC 1-10%
Irgacure 500 1-5%
[0027] Example 7
Figure imgf000010_0001
[0028] Generally, it is known in the art that chlorinated materials such as chlorinated polyester or chlorinated
polyolefins are designed to promote adhesion to specific substances. These substances include polyester, polypropylene, and other thermoplastic olefins (TPO) . EVA is different from and not related to these categories of materials. Therefore, the compositions of the present invention demonstrated the unexpected result of being highly effective with use on EVA as a primer and adhesive.
[0029] . It is believed that these formulations differ from current commercial formulations in omitting tri-functional acrylates and instead using mono and di-functional acrylate monomers. This allows the primer to retain thermoplasticity which allows the cured primer to flow more and wet with the PU/adhesive coated substrate after heat activation compared to prior art compositions. The tri-functional acrylates crosslink more than mono and di-functional acrylates, thus not being very flowable when attempting to bond to the heat activated adhesive surface. It is notable as well that EVA primers in the prior art utilize a solvent base, and are not 100% solids compositions .
[0030]Additionally, compared to the existing solvent borne formulations, this invention is also thicker, because the solvent borne formulations tend to lay down only a monolayer as the solvent is driven off, leaving only solids. With 100% solid formulations, everything disposed on the EVA material remains. This allows better surface wet-out and penetration at the primed surface/adhesive interface. Overall, there is much more contact between layers compared to a thin monolayer with prior art solvent based compositions.
[0031 ] In one embodiment of use, as illustrated in Figure 1, the composition may be applied to an EVA surface, such as a sole of a shoe. This application may be by, for example, spraying, brushing, rolling, or the like. The inventive composition may then be radiation cured- typically UV cured. Once cured the surface is ready to be bonded with an adhesive, for example a polyurethane adhesive-coated upper shoe portion. This adhesive is then used to join the EVA with the mating surface. Optionally, an adhesive may be coated over the cured adhesive/primer of the present invention, but this additional adhesive is not required. Not including this second adhesive application cuts out a step when compared to the prior art process. It should be understood that this embodiment of use may use any variation of the inventive compositions disclosed herein without straying from the scope of this invention.
[0032] While several variations of the present invention have been illustrated by way of example in preferred or particular embodiments, it is apparent that further embodiments could be developed within the spirit and scope of the present
invention, or the inventive concept thereof. However, it is to be expressly understood that such modifications and
adaptations are within the spirit and scope of the present invention, and are inclusive, but not limited to the following appended claims as set forth. It is further to be understood that various aspects and embodiments may include elements and/or components that are similarly and equally applicable to other aspects and embodiments, without being limited to the particular aspect or embodiment to which they are described.

Claims

What is claimed is:
1. A 100% solids composition operable at room temperature and capable of radiation curing comprising:
a monomer, selected to be at least one of a (meth) acrylate monomer and (meth) acrylate functional urethane oligomer ;
a chlorinated compound selected to be at least one of a chlorinated polyester, chlorinated rubber, and chlorinated polyolefin; and
a photo initiator making up to 5% of the composition.
2. The 100% solids composition of claim 1 consisting of:
10-50% hexanediol diacrylate as the monomer;
10-40% chlorinated polyester as the chlorinated compound;
10-30% cyclic aliphatic diacrylate;
1-5% acidic methacrylate ; and
1-5% photoinitiator .
3. The 100% solids composition of claim 1 consisting of:
10-50% hexanediol diacrylate as the monomer;
10-40% chlorinated polyester as the chlorinated compound;
10-30% cyclic aliphatic diacrylate; 1-5% acidic methacrylate ;
5-35% modified epoxy diacrylate; and
1-5% photoinitiator .
The 100% solids composition of claim 1 consisting of:
60-99% methyl methacrylate as the monomer;
0-20% hexanediol diacrylate;
10-20% chlorinated polyolefin as the chlorinated compound;
1-20% acidic methacrylate;
1-5% NVC; and
1-5% photoinitiator .
The 100% solids composition of claim 1 consisting of:
10-30% hexanediol diacrylate as the monomer;
10-70% acrylic polymer;
10-20% chlorinated polyester as the chlorinated compound; 1-5% acidic methacrylate; and
1-5% photoinitiator .
The 100% solids composition of claim 1 consisting of:
10-40% hexanediol diacrylate as the monomer;
10-40% chlorinated polyester as the chlorinated compound; 10-20% cyclic aliphatic diacrylate;
10-20% BCEA;
1-10% NVC; and 1-5% photoinitiator .
7. The 100% solids composition of claim 1 consisting of:
10-40% hexanediol diacrylate as the monomer;
10-40% chlorinated polyester resin as the chlorinated compound;
1-5% acidic methacrylate;
10-20% BCEA;
1-10% NVC; and
1-5% photoinitiator .
8. The 100% solids composition of claim 1 further comprising 10-50 % of the monomer, the monomer being at least one of hexanediol diacrylate and methyl methacrylate.
9. The 100% solids composition of claim 8 further comprising a plurality of different (meth) acrylate functional urethane oligomers, the combination of the plurality of different
(meth) acrylate functional urethane oligomers making up 11- 75% of the composition.
10. The 100% solids composition of claim 8 further comprising the chlorinated compound in a composition of 10-40%.
11. The 100% solids composition of claim 10 further comprising a plurality of different (meth) acrylate functional urethane oligomers.
12. The 100% solids composition of claim 11 wherein the plurality of oligomers comprises cyclic aliphatic diacrylate and acidic methacrylate .
13. The 100% solids composition of claim 11 wherein the plurality of oligomers comprises cyclic aliphatic diacrylate, acidic methacrylate, and modified epoxy diacrylate .
14. The 100% solids composition of claim 8 further comprising 10-30% cyclic aliphatic diacrylate.
15. A method of adhering ethylene-vinyl acetate to a substrate using the composition of claim 1 comprising the steps of :
obtaining the substrate;
obtaining the ethylene-vinyl acetate;
applying the composition of claim 1 at room temperature to the ethylene-vinyl acetate;
contacting the ethylene-vinyl acetate having the composition of claim 1 applied to the substrate; and curing the composition of claim 1 using a radiation.
16. The method of claim 15 wherein the composition further comprises 10-50 % of the monomer, the monomer being at least one of hexanediol diacrylate and methyl methacrylate.
17. The method of claim 16 wherein the composition further comprises a plurality of different (meth) acrylate functional urethane oligomers, the combination of the plurality of different (meth) acrylate functional urethane oligomers making up 11-75% of the composition.
18. The method of claim 16 wherein the composition further comprises the chlorinated compound in a composition of 10-
40% .
19. The method of claim 18 wherein the composition further comprises a plurality of different (meth) acrylate functional urethane oligomers.
20. The method of claim 16 wherein the composition further comprises 10-30% cyclic aliphatic diacrylate.
PCT/US2017/040793 2016-07-06 2017-07-06 Radiation curable primer adhesive Ceased WO2018009591A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP17824844.9A EP3481902A4 (en) 2016-07-06 2017-07-06 RADIATION-BASED PRIMER ADHESIVE
CN201780041776.XA CN109476929B (en) 2016-07-06 2017-07-06 Radiation curable primer binders
US16/238,829 US11174414B2 (en) 2016-07-06 2019-01-03 Radiation curable primer adhesive
US17/500,369 US20220041892A1 (en) 2016-07-06 2021-10-13 Radiation curable primer adhesive

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201662359038P 2016-07-06 2016-07-06
US62/359,038 2016-07-06

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US16/238,829 Continuation US11174414B2 (en) 2016-07-06 2019-01-03 Radiation curable primer adhesive

Publications (1)

Publication Number Publication Date
WO2018009591A1 true WO2018009591A1 (en) 2018-01-11

Family

ID=60913178

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2017/040793 Ceased WO2018009591A1 (en) 2016-07-06 2017-07-06 Radiation curable primer adhesive

Country Status (4)

Country Link
US (2) US11174414B2 (en)
EP (1) EP3481902A4 (en)
CN (1) CN109476929B (en)
WO (1) WO2018009591A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020212488A1 (en) 2019-04-18 2020-10-22 Sun Chemical Corporation Low migration electronic beam curable primer
TWI725645B (en) * 2018-12-03 2021-04-21 法商阿科瑪法國公司 Curable heat-seal adhesives for bonding polymers

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111810735B (en) * 2020-07-27 2021-10-15 漯河市久隆液压科技有限公司 Steel wire braided rubber hose with excellent pulse resistance for engineering machinery
KR20230157299A (en) * 2021-03-18 2023-11-16 시카 테크놀러지 아게 Adhesive bonding method for automated processes

Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3325444A (en) * 1964-07-10 1967-06-13 American Cyanamid Co Stabilized methyl methacrylate monomer and polymer compositions containing a dithio phosphinic acid or a metal salt thereof
US3741253A (en) * 1971-03-30 1973-06-26 Grace W R & Co Laminates of ethylene vinyl acetate polymers and polymers of vinylidene chloride
US3808293A (en) * 1972-01-05 1974-04-30 Du Pont Vinyl chloride polymer,acrylic polymer and acrylonitrile/butadiene/styrene polymer compositions
US4822838A (en) * 1986-11-18 1989-04-18 Osaka Soda Co., Ltd. Curable chlorinated polyethylene and copolyethylene composition
US5124381A (en) * 1990-11-08 1992-06-23 Armstrong World Industries, Inc. Acrylic polymer coating compositions for coats and films that have reduced surface resistivity
US5166254A (en) * 1990-12-03 1992-11-24 E. I. Du Pont De Nemours And Company Waterbased coating composition of methylol (meth)acrylamide acrylic polymer, acrylic hydrosol and melamine crosslinking agent
US5258225A (en) * 1990-02-16 1993-11-02 General Electric Company Acrylic coated thermoplastic substrate
US5492963A (en) * 1994-01-11 1996-02-20 Lord Corporation Overcoat and adhesive compositions based on chlorinated polyolefins having high chlorine contents
EP0544052B1 (en) * 1991-11-27 1996-09-04 Daicel-Ucb Co., Ltd. Use of a photocurable resin composition for the preparation of a laminated film.
US6500877B1 (en) 1999-11-05 2002-12-31 Krohn Industries, Inc. UV curable paint compositions and method of making and applying same
US20040152799A1 (en) * 2003-01-31 2004-08-05 Miller Christopher Wayne Flexible radiation curable compositions
US20050147919A1 (en) * 2002-01-29 2005-07-07 Martin Kunz Process for the production of strongly adherent coatings
EP1686155A1 (en) 2003-11-06 2006-08-02 Toyo Kasei Kogyo Company Limited Ultraviolet curing resin composition, paint, ink, adhesive, sealing agent and primer
US20060247326A1 (en) * 2003-09-25 2006-11-02 Guenter Henke Adhesive composition with barrier characteristics
US20080299478A1 (en) * 2007-05-31 2008-12-04 Xerox Corporation Toner compositions
US20120058317A1 (en) 2010-09-03 2012-03-08 Michelman, Inc. Energy curable primer coating
US20150190331A1 (en) 2014-01-09 2015-07-09 Pakaly Enterprise Co., Ltd. Nail lacquer composition with hyposensitivity

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5237082A (en) 1989-09-22 1993-08-17 Minnesota Mining And Manufacturing Company Radiation-curable silicone elastomers and pressure sensitive adhesives
WO1997003143A1 (en) 1995-07-10 1997-01-30 Minnesota Mining And Manufacturing Company Screen printable adhesive compositions
ES2120387B1 (en) 1996-04-03 1999-09-16 Invest Para La Ind Del Calzado MODIFICATIONS INTRODUCED IN THE MAIN PATENT P 9600792 TITLED "PROCEDURE FOR GLUING THE FLOOR TO THE CUT IN FOOTWEAR, AND OF LEATHER MATERIALS".
AU2274097A (en) 1996-10-08 1998-05-05 Minnesota Mining And Manufacturing Company Primer composition and bonding of organic polymeric substrates
US20070184742A1 (en) 2005-10-20 2007-08-09 Sustainable Solutions, Inc., (SSI) Corp. of Delaware Composite leather material
CN101405352A (en) 2006-03-31 2009-04-08 三井化学株式会社 Photocurable coating material
US20080152829A1 (en) * 2006-12-20 2008-06-26 Dean Roy E Coating compositions, coatings formed therefrom and methods of making the same
US8242224B2 (en) 2007-08-15 2012-08-14 Isp Investments Inc. Polyvinylamide polymers containing polymerizable functionalities
US10590299B2 (en) 2010-06-01 2020-03-17 Riken Technos Corp. Paint, adhesive composition, bonding method and laminate
JP5368635B2 (en) 2010-06-25 2013-12-18 リケンテクノス株式会社 Coating composition for solar cell backsheet and solar cell backsheet
CA2800935A1 (en) * 2010-07-30 2012-02-02 Dsm Ip Assests B.V. D1486 low gloss radiation curable coating for concrete floors
US20130273359A1 (en) 2010-11-26 2013-10-17 Bayer Intellectual Property Gmbh Use of aqueous dispersions as primers
EP2682444A1 (en) 2012-07-06 2014-01-08 Bostik SA Use of an adhesive composition to provide a bonding in a wet environment

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3325444A (en) * 1964-07-10 1967-06-13 American Cyanamid Co Stabilized methyl methacrylate monomer and polymer compositions containing a dithio phosphinic acid or a metal salt thereof
US3741253A (en) * 1971-03-30 1973-06-26 Grace W R & Co Laminates of ethylene vinyl acetate polymers and polymers of vinylidene chloride
US3808293A (en) * 1972-01-05 1974-04-30 Du Pont Vinyl chloride polymer,acrylic polymer and acrylonitrile/butadiene/styrene polymer compositions
US4822838A (en) * 1986-11-18 1989-04-18 Osaka Soda Co., Ltd. Curable chlorinated polyethylene and copolyethylene composition
US5258225A (en) * 1990-02-16 1993-11-02 General Electric Company Acrylic coated thermoplastic substrate
US5124381A (en) * 1990-11-08 1992-06-23 Armstrong World Industries, Inc. Acrylic polymer coating compositions for coats and films that have reduced surface resistivity
US5166254A (en) * 1990-12-03 1992-11-24 E. I. Du Pont De Nemours And Company Waterbased coating composition of methylol (meth)acrylamide acrylic polymer, acrylic hydrosol and melamine crosslinking agent
EP0544052B1 (en) * 1991-11-27 1996-09-04 Daicel-Ucb Co., Ltd. Use of a photocurable resin composition for the preparation of a laminated film.
US5492963A (en) * 1994-01-11 1996-02-20 Lord Corporation Overcoat and adhesive compositions based on chlorinated polyolefins having high chlorine contents
US6500877B1 (en) 1999-11-05 2002-12-31 Krohn Industries, Inc. UV curable paint compositions and method of making and applying same
US20050147919A1 (en) * 2002-01-29 2005-07-07 Martin Kunz Process for the production of strongly adherent coatings
US20040152799A1 (en) * 2003-01-31 2004-08-05 Miller Christopher Wayne Flexible radiation curable compositions
US20060247326A1 (en) * 2003-09-25 2006-11-02 Guenter Henke Adhesive composition with barrier characteristics
EP1686155A1 (en) 2003-11-06 2006-08-02 Toyo Kasei Kogyo Company Limited Ultraviolet curing resin composition, paint, ink, adhesive, sealing agent and primer
US20080299478A1 (en) * 2007-05-31 2008-12-04 Xerox Corporation Toner compositions
US20120058317A1 (en) 2010-09-03 2012-03-08 Michelman, Inc. Energy curable primer coating
US20150190331A1 (en) 2014-01-09 2015-07-09 Pakaly Enterprise Co., Ltd. Nail lacquer composition with hyposensitivity

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3481902A4

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI725645B (en) * 2018-12-03 2021-04-21 法商阿科瑪法國公司 Curable heat-seal adhesives for bonding polymers
WO2020212488A1 (en) 2019-04-18 2020-10-22 Sun Chemical Corporation Low migration electronic beam curable primer
JP2022524226A (en) * 2019-04-18 2022-04-28 サン ケミカル コーポレイション Low migration electron beam curing primer
JP7237199B2 (en) 2019-04-18 2023-03-10 サン ケミカル コーポレイション Low migration electron beam curing primer

Also Published As

Publication number Publication date
US20190194495A1 (en) 2019-06-27
US20220041892A1 (en) 2022-02-10
EP3481902A4 (en) 2020-03-25
CN109476929A (en) 2019-03-15
US11174414B2 (en) 2021-11-16
EP3481902A1 (en) 2019-05-15
CN109476929B (en) 2022-01-25

Similar Documents

Publication Publication Date Title
US20220041892A1 (en) Radiation curable primer adhesive
TWI761604B (en) Reinforcing film
JP6363627B2 (en) Hot melt adhesive containing cyanoacrylate curable compound
KR102236284B1 (en) Reactive 2-component adhesive system
CN110325612B (en) Wrappable and stampable adhesive film
TWI752924B (en) Adhesion Method, Adhesion Structure, and Adhesion Kit
KR102057029B1 (en) Thermally conductive sheet
WO2008093398A1 (en) Process for production of shoes and shoes
CN113166341A (en) Curable heat seal adhesive for bonding polymers
JP2015507662A (en) Dry bondable acrylate adhesive layer
JP2018513231A (en) Optical pressure-sensitive adhesive composition and optical pressure-sensitive adhesive film
WO2015131938A1 (en) Adhesive-coated thermally sensitive polymer substrate, process for its manufacture and use thereof
KR101651718B1 (en) Preparation method for pressure sensitive adhesive article
KR20200026463A (en) Thermal-reactive adhesive film for adhesion process of recycling upper leathers
KR101399329B1 (en) Primer for industry rubber
CN1792651A (en) Inner decoration material for vehicle
CN106381119A (en) Adhesive for PVC (polyvinyl chloride) thin film and preparation method thereof
JP2018150521A (en) Surface protective tape
EP2702889A1 (en) Footwear parts gluing process using powder adhesive
JP2002036368A (en) Wood veneer sticking method
KR101224972B1 (en) Primer composition for non-slip rubber and adhesion method of non-slip rubber by using the same
KR101878527B1 (en) Composition for optical adhesive and bonding film and adhesive and bonding film
KR101693076B1 (en) Adhesive film for encapsulating organic light emitting region and oled display apparatus prepared using the same
JP2002052509A (en) Wood veneer sticking method
CN105705601B (en) Reactive two-component adhesive system

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17824844

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2017824844

Country of ref document: EP

Effective date: 20190206